Phthalocyanine compounds, process for production thereof and electrophotographic photosensitive member using the compounds

ABSTRACT

Iodogallium phthalocyanine and bromogallium phthalocyanine having novel crystalline forms characterized by X-ray diffraction patterns according to CuKalpha characteristic X-ray diffraction method and exhibiting excellent zirconium phthalocyanine can be obtained through appropriate selection of a reaction solvent, followed by milling or stirring in an appropriate solvent. For example, alpha-chloronaphthalene is a suitable solvent for reaction between phthalonitrile and gallium triiodide or tribromide to provide iodogallium phthalocyanine or bromogallium phthalocyanine. Reaction of chlorogallium phthalocyanine or hydroxygallium phthalocyanine with hydroiodic (or hydrobromic) acid is also effective for providing a novel crystal form of iodo- (or bromo-)gallium phthalocyanine. Zirconium phthalocyanine exhibiting good electrophotographic performances can be obtained through a similar process.

FIELD OF THE INVENTION AND RELATED ART

The present invention relates to phthalocyanine compounds, morespecifically iodogallium phthalocyanine compound, bromogalliumphthalocyanine compound and zirconium phthalocyanine compound, havingnovel crystal forms. The present invention further relates to a processfor producing the phthalocyanine compounds and an electrophotographicphotosensitive member using the phthalocyanine compounds.

Hitherto, phthalocyanine pigments have been noted and studied not onlyas coloring agents but also as electronic materials for constitutingelectrophotographic photosensitive members, solar batteries,photosensors, etc.

On the other hand, non-impact type printers utilizing electrophotographyhave been widely used as terminal printers in recent years, in place ofconventional impact type printers. These printers are principallyconstituted as laser beam printers using a laser as a light source. Asthe light source, a semiconductor laser has been predominantly used inview of its cost and apparatus size. A semiconductor laser principallyused at present has an emission wavelength in a long wavelength regionaround 790 nm, so that electrophotographic photoconductors having asufficient sensitivity to such a long-wavelength light have beendeveloped.

The sensitivity region of an electrophotographic photoconductorprincipally varies depending on a charge-generating material, and manystudies have been made on charge-generating materials having asensitivity to a long-wavelength light including metallicphthalocyanines and non-metallic phthalocyanines, such as aluminumchlorophthalocyanine, chloroindium phthalocyanine, oxyvanadiumphthalocyanine, hydroxygallium phthalocyanine, chlorogalliumphthalocyanine, magnesium phthalocyanine, and oxytitaniumphthalocyanine.

Many of these phthalocyanine compounds are known to have various crystalforms. For example, non-metallic phthalocyanine is known to have α-form,β-form, γ-form, δ-form, ε-form, χ-form, τ-form, etc., and copperphthalocyanine is known to have α-form, β-form, γ-form, ε-form, χ-form,etc. Specific examples of these phthalocyanine compounds are disclosedin, e.g., Japanese Laid-Open Patent Application (JP-A) 50-38543, JP-A51-108847, and JP-A 53-37423. Oxytitaniun phthalocyanines are reportedin JP-A 61-217050, JP-A 61-239248, JP-A 62-67094, JP-A 64-17066 and JP-A3-128973. Further, gallium phthalocyanines are disclosed in JP-A 5-98181and JP-A 5-263007 with respect to chlorogallium phthalocyanine andhydroxygallium phthalocyanine together with their crystal forms.Further, iodogallium phthalocyanine is disclosed in JP-A 60-59354, andbromogallium phthalocyanine is disclosed in JP-A 57-148745 but with nospecific disclosure regarding their crystal forms.

However, many electrophotographic photosensitive members using suchknown phthalocyanine compounds only show a low sensitivity and areliable to cause fluctuation in dark-part potential and light-partpotential during repetitive use.

SUMMARY OF THE INVENTION

An object of the present invention is to provide phthalocyaninecompounds having a novel crystal form, and a process producing thecompounds.

Another object of the present invention is to provide anelectrophotographic photosensitive member having a very high sensitivityto long-wavelength light and having excellent potential stability.

According to the present invention, there is provided iodogalliumphthalocyanine having a crystal form selected from those characterizedby X-ray diffraction patterns (a)-(e) shown below respectively obtainedby a CuKα characteristic X-ray diffraction method:

(a) having a strongest peak at a Bragg angle (2θ±0.2 deg.) of 9.6 deg.and free from another peak having an intensity of 30% or more of that ofthe strongest peak,

(b) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 9.4 deg. and 27.1 deg. wherein the second strongestpeak has an intensity of at least 30% of that of the strongest peak,

(c) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 7.5 deg. and 27.7 deg.,

(d) having a strongest peak and a second strongest peak at Bragg angles(20θ±0.2 deg.) of 7.5 deg. and 26.4 deg., and

(e) having two peaks among a strongest peak, a second strongest peak anda third strongest peak at Bragg angles (2θ±0.2 deg.) of 8.8 deg. and27.2 deg.

According to the present invention, there is also provided bromogalliumphthalocyanine having a crystal form selected from those represented byX-ray diffraction patterns (f)-(j) shown below respectively obtained bya CuKα characteristic X-ray diffraction method:

(f) having a strongest peak at a Bragg angle (2θ±0.2 deg.) of 27.3 deg.and free from another peak having an intensity of 30% or more of that ofthe strongest peak,

(g) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 9.0 deg. and 27.1 deg., wherein the second strongestpeak has an intensity of at least 30% of that of the strongest peak,

(h) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 7.4 deg. and 27.9 deg.,

(i) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 7.5 deg. and 26.4 deg., and

(j) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 6.9 deg. and 26.7 deg.

Such iodo- (or bromo-)gallium phthalocyanine may effectively be producedthrough a process comprising: reacting chlorogallium phthalocyanine orhydroxygallium phthalocyanine with hydroiodic (or hydrobromic) acidunder milling or stirring.

According to the present invention, there is further provided zirconiumphthalocyanine having a crystal form represented by an X-ray diffractionpattern having a strongest peak at a Bragg angle (2θ±0.2 deg.) in arange of 7.0-9.0 deg. as measured by a CuKα characteristic X-raydiffraction method.

Such zirconium phthalocyanine may effectively be produced through aprocess comprising milling or stirring zirconium phthalocyanine in anorganic solvent.

According to the present invention, there is also provided anelectrophotographic photosensitive member, comprising a support, and aphotosensitive layer formed on the support and containing one of theabove-mentioned iodogallium phthalocyanine, bromogallium phthalocyanineand zirconium phthalocyanine.

These and other objects, features and advantages of the presentinvention will become more apparent upon a consideration of thefollowing description of the preferred embodiments of the presentinvention taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 are sectional views each showing an example of laminarstructure of an electrophotographic photosensitive member.

FIGS. 3-31 each show an X-ray diffraction pattern of an iodogalliumphthalocyanine crystal according to the invention.

FIGS. 32-59 each show an X-ray diffraction pattern of a bromogalliumphthalocyanine crystal according to the invention.

FIGS. 60-75 each show an X-ray diffraction pattern of a zirconiumphthalocyanine according to the invention.

FIGS. 76 and 77 each show an infrared absorption spectrum of zirconiumphthalocyanine according to the invention.

FIG. 78 schematically illustrates an electrophotographic apparatus inwhich a process cartridge including an electrophotographicphotosensitive member according to the invention is mounted.

DETAILED DESCRIPTION OF THE INVENTION

The iodogallium phthalocyanine according to the present invention has acrystal form selected from those characterized by X-ray diffractionpatterns (a)-(e) shown below respectively obtained by a CuKαcharacteristic X-ray diffraction method:

(a) having a strongest peak at a Bragg angle (2θ±0.2 deg.) of 9.6 deg.and free from another peak having an intensity of 30% or more of that ofthe strongest peak,

(b) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 9.4 deg. and 27.1 deg. wherein the second strongestpeak has an intensity of at least 30% of that of the strongest peak,

(c) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 7.5 deg. and 27.7 deg.,

(d) having a strongest peak and a second strongest peak at Bragg angles(29θ±0.2 deg.) of 7.5 deg. and 26.4 deg., and

(e) having two peaks among a strongest peak, a second strongest peak anda third strongest peak at Bragg angles (2θ±0.2 deg.) of 8.8 deg. and27.2 deg.

It is preferred that the diffraction pattern (b) further has strongpeaks at Bragg angles (2θ±0.2 deg.) of 8.7 deg., 16.4 deg., 18.3 deg.and 27.2 deg.

It is preferred that the diffraction pattern (c) further has a strongpeak at a Bragg angle (2θ±0.2 deg.) of 16.3 deg.

It is also preferred that the diffraction pattern (d) further has astrong peak at a Bragg angle (2θ±0.2 deg.) of 16.3 deg.

It is also preferred that the diffraction pattern (e) further has astrong peak at a Bragg angle (2θ±0.2 deg.) of 9.8 deg.

The iodogallium phthalocyanine according to the present invention has astructure represented by the following formula:

wherein X₁, X₂, X₃ and X₄ denote Cl or Br, n₁, m₁, p, and k₁ arerespectively an integer of 0-4.

Iodogallium phthalocyanine may for example be formed by reactingphthalocyanine and gallium triiodide in α-chloronaphthalene solvent at150-230° C. It has been also discovered that iodogallium phthalocyaninecan be obtained by reacting chlorogallium phthalocyanine obtainedthrough various process, e.g., one shown in JP-A 5-194523 orhydroxygallium phthalocyanine formed by hydrolyzing the chlorogalliumphthalocyanine with hydroiodic acid under application of a shearingforce, as by milling or stirring. This process is commercially desirablebecause inexpensive gallium chloride can be used instead of galliumiodide. The iodogallium phthalocyanine prepared according to the processis in an amorphous form.

More specifically, iodogallium phthalocyanine having a crystal formrepresented by a diffraction pattern (a) showing a strong peak at aBragg angle (2θ±0.2 deg.) of 9.7 deg. (hereinafter, sometimes referredas “iodogallium phthalocyanine (a)”) may be formed by reactingphthalonitrile and gallium triiodide in a reaction solvent ofα-chloronaphthalene under stirring and heating at 150-230° C. It ispossible to further subject the product iodogallium phthalocyanine towashing under heating dispersion within an amide solvent, such asN,N-dimethylformamide, or washing with an alcohol, such as ethanol. Thecrystal form is not changed by such washing.

Iodogallium phthalocyanine having a crystal form represented by adiffraction pattern (b) having strong peaks at Bragg angles (2θ±0.2deg.) of 9.4 deg. and 27.1 deg. (hereinafter sometimes referred to as“iodogallium phthalocyanine (b)”) may be obtained by subjectingiodogallium phthalocyanine (a) to dry milling exerting a relatively weakshearing force, as by a mortar.

Iodogallium phthalocyanine (b) may also be prepared by subjecting (i)amorphous iodogallium phthalocyanine prepared by milling or stirringchlorogallium phthalocyanine or hydroxygallium phthalocyanine togetherwith hydroiodic acid, or (ii) iodogallium phthalocyanine (a), to drymilling exerting a relatively large shearing force, as by a sand mill ora paint shaker together with glass beads to obtain a crystal, andsubjecting the crystal to milling in an appropriate solvent, examples ofwhich may include: halogen-containing solvents, such as chloroform,chlorobenzene and dichlorobenzene; ketone solvents, such as cyclohexane,methyl ethyl ketone and acetone; nitrile solvents, such as acetonitrileand benzonitrile; ester solvents, such as ethyl acetate and butylacetate; alcohol solvents, such as methanol, ethanol, propanol, ethyleneglycol and polyethylene glycol, and ether solvents, such astetrahydrofuran, 1,4-dioxane, propyl ether, and butyl ether. By millingor stirring iodogallium phthalocyanine in such a solvent, it is possibleto obtain iodogallium phthalocyanine (b) in various crystallinities.

Iodogallium phthalocyanine having a crystal form represented by adiffracting pattern (c) showing strong peaks at Bragg angles (2θ±0.2deg) of 7.5 deg and 27.7 deg. (hereinafter sometimes referred as“iodogallium phthalocyanine (c)) may be obtained by milling or stirring(i) a crystal formed by subjecting iodogallium phthalocyanine (a) to drymilling, as by a mortar, a sand mill, a ball mill, or a paint shaker, or(ii) amorphous iodogallium phthalocyanine obtained in the mannerdescribed above, in an amide solvent, such as N,N-dimethylformamide, orN-methylpyrrolidone.

Iodogallium phthalocyanine having a crystal form represented by adiffraction pattern (d) showing strong peaks at Bragg angles (2θ±0.2deg.) of 7.5 deg. and 26.4 deg. (hereinafter sometimes referred to as“iodogallium phthalocyanine (d)”) may be obtained by milling or stirring(i) a crystal formed by subjecting iodogallium phthalocyanine (a) to drymilling, as by a mortar, a sand mill, a ball mill, or a paint shaker, or(ii) amorphous iodogallium phthalocyanine obtained in the mannerdescribed above, in an amine solvent, such as N,N-dimethylaniline,N,N-diethylaniline or quinoline.

Iodogallium phthalocyanine having a crystal form represented by adiffraction pattern (e) showing strong peaks at Bragg angles (2θ±0.2deg.) of 8.8 deg. and 27.1 deg. may be obtained by subjectingiodogallium phthalocyanine (a) to dry milling, as by a mortar, a sandmill or a paint shaker, or by stirring the above-mentioned amorphousiodogallium phthalocyanine in water.

Herein, “milling” means a treatment by using a milling device, such as asandmill, a ball mill or a paint shaker together with dispersion media,such as glass beads, steel beads or alumina beads. On the other hand,“stirring” means a stirring treatment without using such dispersionmedia.

The bromogallium phthalocyanine according to the present invention has acrystal form selected from those represented by X-ray diffractionpatterns (f)-(j) shown below respectively obtained by a CuKαcharacteristic X-ray diffraction method:

(f) having a strongest peak at a Bragg angle (2θ±0.2 deg.) of 27.3 deg.and free from another peak having an intensity of 30% or more of that ofthe strongest peak,

(g) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 9.0 deg. and 27.1 deg., wherein the second strongestpeak has an intensity of at least 30% of that of the strongest peak,

(h) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 7.4 deg. and 27.9 deg.,

(i) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 7.5 deg. and 26.4 deg., and

(j) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 6.9 deg. and 26.7 deg.

It is preferred that the diffraction pattern (g) further shows strongpeaks at Bragg angles (2θ±0.2 deg.) of 9.7 deg., 18.2 deg. and 21.0deg.; the diffraction pattern (h) further shows a strong peak at a Braggangle (2θ±0.2 deg.) of 16.2 deg.; the diffraction pattern (i) furthershows strong peaks at Bragg angles (2θ±0.2 deg.) of 16.3 deg. and 24.9deg.; and the diffraction pattern (j) further shows strong peaks atBragg angles (2θ±0.2 deg.) of 13.2 deg. and 16.6 deg.

The bromogallium phthalocyanine according to the present invention has astructure represented by the following formula:

wherein X₅, X₆, X₇ and X₈ denote Cl or Br, n₂, m₂, p₂ and k₂ arerespectively an integer of 0-4.

The above-mentioned bromogallium phthalocyanine may for example beformed by reacting phthalocyanine and gallium tribromide inα-chloronaphthalene solvent at 150-230° C. It has been also discoveredthat bromogallium phthalocyanine can be obtained by reactingchlorogallium phthalocyanine obtained through various process, e.g., onedisclosed in JP-A 5-194523 or hydroxygallium phthalocyanine formed byhydrolyzing the chlorogallium phthalocyanine with hydrobromic acid underapplication of a shearing force, as by milling or stirring. This processis commercially desirable because inexpensive gallium chloride can beused instead of gallium bromide.

More specifically, bromogallium phthalocyanine having a crystal formrepresented by a diffraction pattern (f) showing a strong peak at aBragg angle (2θ±0.2 deg.) of 27.3 deg. (hereinafter, sometimes referredas “bromogallium phthalocyanine (f)”) may be formed by reactingphthalonitrile and gallium tribromide in a reaction solvent ofα-chloronaphthalene under stirring and heating at 150-230° C. It ispossible to further subject the product bromogallium phthalocyanine towashing under heating dispersion within an amide solvent, such asN,N-dimethylformamide, or washing with an alcohol, such as ethanol. Thecrystal form is not changed by such washing.

Bromogallium phthalocyanine having a crystal form represented by adiffraction pattern (g) having strong peaks at Bragg angles (2θ±0.2deg.) of 9.0 deg. and 27.1 deg. (hereinafter sometimes referred to as“bromogallium phthalocyanine (g)”) may be obtained by subjectingbromogallium phthalocyanine (f) to dry milling by a mortar.

Bromogallium phthalocyanine (g) may also be prepared by subjectingbromogallium phthalocyanine (f), to dry milling, as by a sand mill or apaint shaker together with glass beads to obtain a crystal, andsubjecting the crystal to milling in an appropriate solvent, examples ofwhich may include: halogen-containing solvents, such as chloroform,chlorobenzene and dichlorobenzene; ketone solvents, such as cyclohexane,methyl ethyl ketone and acetone; nitrile solvents, such as acetonitrileand benzonitrile; ester solvents, such as ethyl acetate and butylacetate, alcohol solvents, such as methanol, ethanol, propanol, ethyleneglycol and polyethylene glycol, and ether solvents, such astetrahydrofuran, 1,4-dioxane, propyl ether, and butyl ether. By millingor stirring bromogallium phthalocyanine in such a solvent, it ispossible to obtain bromogallium phthalocyanine (g) in variouscrystallinities.

Bromogallium phthalocyanine having a crystal form represented by adiffracting pattern (h) showing strong peaks at Bragg angles (2θ±0.2deg) of 7.4 deg and 27.9 deg. (hereinafter sometimes referred as“bromogallium phthalocyanine (h)”) may be obtained by subjectingbromogallium phthalocyanine (f) to dry milling, as by a sand mill or apaint shaker, together with glass beads.

Bromogallium phthalocyanine (h) may also be obtained by milling orstirring (i) a crystal formed by subjecting bromogallium phthalocyanine(f) to dry milling, as by a mortar, or (ii) bromogallium phthalocyanine(g) obtained by treatment with hydrobromic acid, in an amide solvent,such as N,N-dimethylformamide, or N-methylpyrrolidone.

Bromogallium phthalocyanine having a crystal form represented by adiffraction pattern (i) showing strong peaks at Bragg angles (2θ±0.2deg.) of 7.5 deg. and 26.4 deg. (hereinafter sometimes referred to as“bromogallium phthalocyanine (i)”) may be obtained by milling orstirring (i) a crystal formed by subjecting bromogallium phthalocyanine(f) to dry milling, as by a mortar, a sand mill, a ball mill, or a paintshaker, or (ii) bromogallium phthalocyanine (g) obtained by treatmentwith hydrobromic acid in an amine solvent, such as N,N-dimethylaniline,N,N-diethylaniline or quinoline.

Bromogallium phthalocyanine having a crystal form represented by adiffraction pattern (j) showing strong peaks at Bragg angles (2θ±0.2deg.) of 6.9 deg. and 26.7 deg. may be obtained by milling or stirringbromogallium phthalocyanine (g) obtained by treatment with hydrobromicacid in a weak alkaline aqueous solution (pH of at most 11), followed bywashing with water.

Zirconium phthalocyanine according to the present invention has acrystal form represented by an X-ray diffraction pattern having astrongest peak at a Bragg angle (2θ±0.2 deg.) in a range of 7.0-9.0 deg.as measured by a CuKα characteristic X-ray diffraction method.

It is preferred that the X-ray diffraction pattern shows a strongestpeak at a Bragg angle (2θ±0.2 deg.) of 8.0 deg. It is further preferredthat the diffraction pattern further shows a strong peak at a Braggangle (2θ±0.2 deg.) of 25.5 deg.

The zirconium phthalocyanine according to the present invention has astructure represented by the following formula:

wherein X₉, X₁₀, X₁₁ and X₁₂ denote Cl or Br, n₃, m₃, p₃ and k₃ arerespectively an integer of 0-4.

The zirconium phthalocyanine may for example be prepared by reactingphthalonitrile and zirconium tetrachloride in an appropriate solvent,such as quinoline, under an inert gas atmosphere at 150-230° C., anddispersing the reaction product in the reaction solvent or a solventsuch as N,N-dimethylformamide. Various forms of zirconium phthalocyaninemay be formed milling or stirring the thus synthesized zirconiumphthalocyanine in an appropriate solvent, directly or after dry-milling,as by a mortar, a sand mill, a ball mill or a paint shaker.

Examples of appropriate solvent may include: halogen-containingsolvents, such as chloroform, chlorobenzene and dichlorobenzene; ketonesolvents, such as cyclohexane, methyl ethyl ketone and acetone; nitrilesolvents, such as acetonitrile and benzonitrile; ester solvents, such asethyl acetate and butyl acetate; alcohol solvents, such as methanol,ethanol, propanol, ethylene glycol and polyethylene glycol; ethersolvents, such as tetrahydrofuran, 1,4-dioxane, propyl ether, and butylether; amine solvents, such as N,N-dimethylaniline andN,N-diethylaniline; and amide solvents, such as N,N-dimethylformamideand N-methylpyrrolidone.

The above-mentioned phthalocyanine compound of the invention functionsas an excellent photoconductor and may be adapted for an electronicmaterial such as an electrophotosensitive member, a solar cell, a sensoror a switching device.

Hereinafter, some examples of application of the phthalocyanine compoundof the invention to a charge-generating material in anelectrophotosensitive member will be explained.

Representative embodiments of laminar structure of theelectrophotosensitive member of the invention are shown in FIGS. 1 and2. FIG. 1 shows an embodiment, wherein a photosensitive layer 1 iscomposed of a single layer and comprises a charge-generating material 2and a charge-transporting material (not shown) together. Thephotosensitive layer 1 may be disposed on an electroconductive support3. FIG. 2 shows an embodiment of laminated structure wherein aphotosensitive layer 1 comprises a charge generation layer 4 comprisinga charge-generating material 2 and a charge transport layer 5 comprisinga charge-transporting material (not shown) disposed on the chargegeneration layer 4; and the charge transport layer 5 may be disposed onan electroconductive support 3. The charge generation layer 4 and thecharge transport layer 5 can be disposed in reverse. The laminarstructure of FIG. 2 is preferred in the present invention.

The electroconductive support 3 may comprise a material having anelectroconductivity including: a metal such as aluminum or stainlesssteel; and metal, plastic or paper having an electroconductive layer.The support 3 may have a shape of a cylinder or a sheet.

Between the electroconductive support 3 and the photosensitive layer 1,there can be formed a primer or undercoat layer having a barrierfunction and an adhesive function as an intermediate layer. The primerlayer may comprise a substance, such as polyvinyl alcohol, polyethyleneoxide, ethyl cellulose, methyl cellulose, casein, polyamide, glue orgelatin. The above substance may be dissolved in an appropriate solventand applied onto the electroconductive support 3 to prepare the primerlayer. The thickness of the primer layer may be 0.2-3.0 μm.

The photosensitive layer which is composed of a single layer as shown inFIG. 2 may be formed by dispersing or dissolving the charge-generatingmaterial comprising the phthalocyanine compound of the invention and thecharge-transporting material with an appropriate solution containing abinder resin, applying the resultant coating liquid and then drying thecoating.

The charge generation layer of the photosensitive layer having alaminated structure as shown in FIG. 2 may be formed by dispersing thecharge-generating material comprising the oxytitanium phthalocyaninecrystal of the invention in an appropriate solution containing a binderresin, applying the resultant coating liquid and then drying thecoating. Examples of the binder resin as described above may include:polyester, acrylic resins, polyvinylcarbazole, phenoxy resins,polycarbonate, polyvinyl butyral, polystyrene, vinyl acetate resins,polysulfone, polyarylate or vinylidene chloride-acrylonitrilecopolymers.

The charge transport layer may be formed by dissolving acharge-transporting material and a binder resin in an appropriatesolvent, applying the resultant coating liquid and then drying thecoating. Examples of the charge-transporting material used may include:triaryl amine compounds, hydrazone compounds, stilbene compounds,pyrazoline compounds, oxazole compounds, thiazole compounds or triarylmethane compounds. As the binder resin, the above-mentioned resins canbe used.

The method for applying the photosensitive layer(s) may be: dipping,spray coating, spinner coating, bead coating, blade coating or beamcoating.

The thickness of the photosensitive layer composed of a single layer maypreferably be 5-40 μm, more preferably 10-30 μm. When the photosensitivelayer has a laminated structure, the thickness of the charge generationlayer may preferably be 0.01-10 μm, more preferably 0.05-5 μm and thethickness of the charge transport layer may preferably be 5-40 μm, morepreferably 10-30 μm.

In order to protect the photosensitive layer from external shock, a thinprotective layer can be further disposed on the photosensitive layer.

When the phthalocyanine compound of the invention is used as thecharge-generating material, it is possible to mix the phthalocyaninecompound with another charge-generating material.

The electrophotographic photosensitive member according to the presentinvention can be applied to not only a laser beam printer, alight-emitting diode (LED) printer and a cathode-ray tube (CRT) printerbut also an ordinary electrophotographic copying machine and otherfields of applied electrophotography.

FIG. 78 shows an outline of an electrophotographic apparatus includingan electrophotographic photosensitive member according to the presentinvention as an essential part of a process cartridge.

Referring to FIG. 78, a drum-shaped electrophotographic photosensitivemember 6 according to the present invention is driven in rotation at aprescribed peripheral speed in an indicated arrow direction about anaxis 7. During the rotation, the outer peripheral surface of thephotosensitive member 6 is uniformly charged at a prescribed positive ornegative potential, and then exposed to image light 9 (as by slitexposure or laser beam scanning exposure) by using an imagewise exposuremeans (not shown), whereby an electrostatic latent image is successivelyformed on the peripheral surface of the photosensitive member 6.

The thus-formed electrostatic latent image is then developed with atoner by developing means 10 to form a toner image on the photosensitivemember 6. The toner image is transferred by a transfer means 11 onto atransfer(-receiving) material 12 which has been supplied from a papersupply unit (not shown) to a position between the photosensitive member6 and the transfer means 11 in synchronism with the rotation of thephotosensitive member 6.

The transfer material 12 carrying the received toner image is thenseparated from the photosensitive member 6 surface and guided to animage fixing means 13 to fix the toner image. The resultant print orcopy comprising the fixed toner image is then discharged out of theelectrophotographic apparatus.

The surface of the photosensitive member after the image transfer issubjected to removal of residual toner by a cleaning means 14 to becleaned and then subjected to charge removal by exposure to pre-exposurelight from a pre-exposure means (not shown) to be recycled forrepetitive image formation. Incidentally, in case where the primarycharging means 8 is a contact charging means, such s a charging roller,the pre-exposure is not necessarily required.

Plural members among the above-mentioned electrophotographicphotosensitive member 6, primary charging means 8, developing means 10and cleaning means 14 may be integrally supported to form a processcartridge so as to be detachably mountable to a main assembly of anelectrophotographic apparatus, such as a copying machine or a laser beamprinter. As shown in FIG. 78, for example, at least one of the primarycharging means 8, the developing means 10 and the cleaning means 14 maybe integrally supported together with the photosensitive member 6 toform a process cartridge 16, which is detachably mountable to anapparatus main assembly with the aid of a guide means, such as a rail 17provided in the apparatus main assembly.

In case where the electrophotographic apparatus is used as a copyingmachine or a printer, exposure image light 9 may be given as reflectedlight from or transmitted light through an original, or as illuminationlight formed by reading data of an original by a sensor to provide asignal and driving a laser beam scanner, an LED array or a liquidcrystal shutter array based on the signal.

Hereinbelow, the present invention will be described more specificallybased on Examples, wherein “parts” used for describing compositions areby weight unless otherwise noted specifically.

Incidentally, X-ray diffraction data described herein as representingvarious crystal forms of phthalocyanine compounds are based on datameasured by X-ray diffractometry using CuK_(α) characteristic X-raysaccording to the following conditions:

Apparatus: Full-automatic X-ray diffraction apparatus (“MXP18”,available from MAC Science K.K.)

X-ray tube (Target): Cu

Tube voltage: 50 kV

Tube current: 300 mA

Scanning method: 2θ/θ scan

Scanning speed: 2 deg./min.

Sampling interval: 0.020 deg.

Starting angle (2θ): 5 deg.

Stopping angle (2θ): 40 deg.

Divergence slit: 0.5 deg.

Scattering slit: 0.5 deg.

Receiving slit: 0.3 deg.

Curved monochromator: used.

EXAMPLE 1

28 parts of phthalonitrile, 25 parts of gallium triiodide and 150 partsof α-chloronaphthalene were stirred for 4 hours under heating at 200° C.in a nitrogen atmosphere, followed by cooling to 130° C. and filtration.The recovered solid was washed with 200 parts of N,N-dimethylformamideat 130° C. under stirring for 2 hours, and was washed with methanol on afilter, followed by drying to 27 parts of a crystal, which was found tocomprise iodogallium phthalocyanine (a) with an X-ray diffractionpattern shown in FIG. 3. The crystal also exhibited the followingelementary analysis results (C₃₂H₁₆N₈GaI):

C (%) H (%) N (%) I (%) Calculated value 54.20 2.27 15.80 17.90 Measuredvalue 54.20 2.21 16.96 17.4 

EXAMPLE 2

5 parts of the crystal obtained in Example 1 was treated for 3 hours inan automatic mortar (“ANM-150” (trade name), available from Nitto KagakuK.K. and comprising a porcelain mortar and a porcelain pestle rotatingat fixed speeds of 6 rpm and 100 rpm, respectively, in mutually reversedirections) to provide a crystal, which was found to compriseiodogallium phthalocyanine (b) with an X-ray diffraction pattern shownin FIG. 4.

EXAMPLE 3

5 parts of the crystal obtained in Example 1 was treated for 9 hours inan automatic mortar identical to the one used in Example 2 to provide acrystal, which was found to comprise iodogallium phthalocyanine (e) withan X-ray diffraction pattern shown in FIG. 5.

EXAMPLE 4

0.3 part of the crystal obtained in Example 2, 10 parts of cyclohexanoneand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol and dryingto recover a crystal, which was found to comprise iodogalliumphthalocyanine (b) with an X-ray diffraction pattern shown in FIG. 6.

EXAMPLE 5

0.3 part of the crystal obtained in Example 2, 10 parts of acetonitrileand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol and dryingto recover a crystal, which was found to comprise iodogalliumphthalocyanine (b) with an X-ray diffraction pattern shown in FIG. 7.

EXAMPLE 6

0.3 part of the crystal obtained in Example 2, 10 parts of butyl acetateand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol and dryingto recover a crystal, which was found to comprise iodogalliumphthalocyanine (b) with an X-ray diffraction pattern shown in FIG. 8.

EXAMPLE 7

0.3 part of the crystal obtained in Example 2, 10 parts of ethyleneglycol and 10 parts of 1 mm-dia. glass beads were dispersed for 24 hoursin a paint shaker, followed by filtration, washing with methanol anddrying to recover a crystal, which was found to comprise iodogalliumphthalocyanine (b) with an X-ray diffraction pattern shown in FIG. 9.

EXAMPLE 8

0.3 part of the crystal obtained in Example 2, 10 parts ofmonochlorobenzene and 10 parts of 1 mm-dia. glass beads were dispersedfor 24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to compriseiodogallium phthalocyanine (b) with an X-ray diffraction pattern shownin FIG. 10.

EXAMPLE 9

0.3 part of the crystal obtained in Example 2, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to compriseiodogallium phthalocyanine (b) with an X-ray diffraction pattern shownin FIG. 11.

EXAMPLE 10

0.3 part of the crystal obtained in Example 2, 10 parts of methyl ethylketone and 10 parts of 1 mm-dia. glass beads were dispersed for 24 hoursin a paint shaker, followed by filtration, washing with methanol anddrying to recover a crystal, which was found to comprise iodogalliumphthalocyanine (b) with an X-ray diffraction pattern shown in FIG. 12.

EXAMPLE 11

0.3 part of the crystal obtained in Example 2, 10 parts of methanol and10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in a paintshaker, followed by filtration, washing with methanol and drying torecover a crystal, which was found to comprise iodogalliumphthalocyanine (b) with an X-ray diffraction pattern shown in FIG. 13.

EXAMPLE 12

0.3 part of the crystal obtained in Example 2, 10 parts ofN,N-dimethylformamide and 10 parts of 1 mm-dia. glass beads weredispersed for 24 hours in a paint shaker, followed by filtration,washing with methanol and drying to recover a crystal, which was foundto comprise iodogallium phthalocyanine (c) with an X-ray diffractionpattern shown in FIG. 14.

EXAMPLE 13

0.3 part of the crystal obtained in Example 2, 10 parts ofN,N-diethylaniline and 10 parts of 1 mm-dia. glass beads were dispersedfor 24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to compriseiodogallium phthalocyanine (d) with an X-ray diffraction pattern shownin FIG. 15.

EXAMPLE 14

3 parts of the crystal obtained in Example 1 and 120 parts of 1 mm-dia.glass beads were dispersed for 24 hours in a paint shaker, followed byan ultrasonic treatment in water, filtration and drying to obtain acrystal, which was found to comprise iodogallium phthalocyanine (e) withan X-ray diffraction pattern of FIG. 16.

EXAMPLE 15

3 parts of the crystal obtained in Example 1 and 120 parts of 1 nm-dia.glass beads were dispersed for 72 hours in a paint shaker, followed byan ultrasonic treatment in water filtration and drying to obtain acrystal, which was found to comprise iodogallium phthalocyanine (e) withan X-ray diffraction pattern of FIG. 17.

EXAMPLE 16

0.3 part of the crystal obtained in Example 14, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to compriseiodogallium phthalocyanine (b) with an X-ray diffraction pattern shownin FIG. 18.

The crystal also exhibited the following elementary analysis results(C₃₂H₁₆N₈GaI):

C (%) H (%) N (%) Calculated value 54.20 2.27 15.80 Measured value 56.042.29 16.05

EXAMPLE 17

0.3 part of the crystal obtained in Example 14, 10 parts of chloroformand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol and dryingto recover a crystal, which was found to comprise iodogalliumphthalocyanine (b) with an X-ray diffraction pattern shown in FIG. 19.

EXAMPLE 18

0.3 part of the crystal obtained in Example 14, 10 parts of methanol and10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in a paintshaker, followed by filtration, washing with methanol and drying torecover a crystal, which was found to comprise iodogalliumphthalocyanine (b) with an X-ray diffraction pattern shown in FIG. 20.

EXAMPLE 19

0.3 part of the crystal obtained in Example 15, 10 parts of methanol and10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in a paintshaker, followed by filtration, washing with methanol and drying torecover a crystal, which was found to comprise iodogalliumphthalocyanine (b) with an X-ray diffraction pattern shown in FIG. 21.

EXAMPLE 20

0.3 part of the crystal obtained in Example 14, 10 parts ofN,N-dimethylaniline and 10 parts of 1 mm-dia. glass beads were dispersedfor 24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to compriseiodogallium phthalocyanine (d) with an X-ray diffraction pattern shownin FIG. 22.

EXAMPLE 21

0.3 part of the crystal obtained in Example 14, 10 parts ofN,N-dimethylformamide and 10 parts of 1 mm-dia. glass beads weredispersed for 24 hours in a paint shaker, followed by filtration,washing with methanol and drying to recover a crystal, which was foundto comprise iodogallium phthalocyanine (c) with an X-ray diffractionpattern shown in FIG. 23.

The crystal also exhibited the following elementary analysis results(C₃₂H₁₆N₈GaI):

C (%) H (%) N (%) Calculated value 54.20 2.27 15.80 Measured value 54.342.63 15.01

EXAMPLE 22

0.3 part of the crystal obtained in Example 15, 10 parts ofN,N-dimethylformamide and 10 parts of 1 mm-dia. glass beads weredispersed for 24 hours in a paint shaker, followed by filtration,washing with methanol and drying to recover a crystal, which was foundto comprise iodogallium phthalocyanine (c) with an X-ray diffractionpattern shown in FIG. 24.

EXAMPLE 23

0.3 part of hydroxygallium phthalocyanine (with an X-ray diffractionpattern of FIG. 25), 10 parts of 1N-hydroiodic acid aqueous solution and10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in a paintshaker, followed by filtration, washing with methanol and drying torecover a solid, which was found to comprise amorphous iodogalliumphthalocyanine with an X-ray diffraction pattern shown in FIG. 26.

EXAMPLE 24

0.3 part of hydroxygallium phthalocyanine (with an X-ray diffractionpattern of FIG. 25), 10 parts of 2N-hydroiodic acid aqueous solution and10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in a paintshaker, followed by filtration, washing with methanol and drying torecover a solid, which was found to comprise amorphous iodogalliumphthalocyanine with an X-ray diffraction pattern shown in FIG. 27.

EXAMPLE 25

0.3 part of the crystal obtained in Example 23, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to compriseiodogallium phthalocyanine (b) with an X-ray diffraction pattern shownin FIG. 28.

The crystal also exhibited the following elementary analysis results(C₃₂H₁₆N₈GaI):

C (%) H (%) N (%) Calculated value 54.20 2.27 15.80 Measured value 54.412.58 18.92

EXAMPLE 26

0.3 part of the crystal obtained in Example 24, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to compriseiodogallium phthalocyanine (b) with an X-ray diffraction pattern shownin FIG. 29.

EXAMPLE 27

0.3 part of the crystal obtained in Example 23, 10 parts ofN,N-dimethylformamide and 10 parts of 1 mi-dia. glass beads weredispersed for 24 hours in a paint shaker, followed by filtration,washing with methanol and drying to recover a crystal, which was foundto comprise iodogallium phthalocyanine (c) with an X-ray diffractionpattern shown in FIG. 30.

EXAMPLE 28

3 parts of the crystal obtained in Example 23 was stirred in 100 partsof water, followed by filtration, washing with methanol and drying torecover a crystal, which was found to comprise iodogalliumphthalocyanine (e) with an X-ray diffraction pattern shown in FIG. 31.

Hereinbelow, some examples for preparation of electrophotographicphotosensitive members by using iodogallium phthalocyanines preparedabove will be described.

EXAMPLE 29

An aluminum substrate was coated with a solution of 5 g ofmethoxymethylated nylon resin (Mw (weight−average molecularweight)=3.2×10⁴) and 10 g of alcohol-soluble copolymer nylon(Mw=2.9×10⁴) in 95 g of methanol by using a wire bar and dried to form a1 μm-thick undercoating layer.

Then, 3 parts of the iodogallium phthalocyanine (a) prepared in Example1 was added to a solution of 2 parts of polyvinylbutyral in 60 parts ofcyclohexanone, and the mixture was dispersed together with 100 parts of1 mm-dia. glass beads for 3 hours in a sand mill. The resultantdispersion was further diluted with 100 parts of ethyl acetate, andapplied by a wire bar over the undercoating layer, followed by drying toform a 0.2 μm-thick charge generation layer.

Then, a solution of 5 parts of a triarylamine compound of the followingformula:

and 5 parts of polycarbonate resin (“Z-200” (trade name), mfd. byMitsubishi Kagaku K.K.) in 35 parts of chlorobenzene was applied by awire bar onto the charge generation layer and dried to form a 18μm-thick charge transport layer, thereby providing anelectrophotographic photosensitive member.

EXAMPLES 30-39

Electrophotographic photosensitive members were prepared in the samemanner as in Example 29 except for using iodogallium phthalocyaninesprepared in the respective Examples shown in Table 1 below as chargegeneration materials instead of iodogallium phthalocyanine (a) preparedin Example 1.

COMPARATIVE Example 1

An electrophotographic photosensitive member was prepared in the samemanner as in Example 29 except for using ε-form copper phthalocyanine asa charge generation material instead of iodogallium phthalocyanine (a)prepared in Example 1.

COMPARATIVE EXAMPLE 2

An electrophotographic photosensitive member was prepared in the samemanner as in Example 29 except for using hydroxygallium phthalocyanine(with an X-ray diffraction pattern of FIG. 25) as a charge generationmaterial instead of iodogallium phthalocyanine (a) prepared in Example1.

Each of the above-prepared photosensitive members was applied onto analuminum cylinder to form a photosensitive drum, which was incorporatedin a laser beam printer (“LBX-SX” (trade name), mfd. by Canon K.K.) andsubjected to a sensitivity measurement wherein the photosensitive memberwas first charged to a dark-part potential of −700 volts and illuminatedwith laser light at a wavelength of 802 nm, thereby measuring a lightquantity required to lower the potential of −700 volts down to alight-part potential of −150 volts as a sensitivity.

The results are inclusively shown in Table 1 below.

TABLE 1 No. of Iodogallium photosensitive phthalocyanine SensitivityExample member (Ex. No.) (μJ/cm²) Ex. 29 1 (a) (Ex. 1)  2.10 Ex. 30 2(b) (Ex. 7)  0.90 Ex. 31 3 (c) (Ex. 12) 0.90 Ex. 32 4 (d) (Ex. 13) 2.20Ex. 33 5 (b) (Ex. 16) 0.85 Ex. 34 6 (b) (Ex. 19) 0.70 Ex. 35 7 (c) (Ex.21) 0.31 Ex. 36 8 (c) (Ex. 22) 0.52 Ex. 37 9 (b) (Ex. 26) 1.95 Ex. 3810  (c) (Ex. 27) 0.42 Ex. 39 11  (e) (Ex. 28) 0.64 Comp. 1 ε-Cu 2.25 Ex.1  Comp. 13  Hydroxygallium ** Ex. 2  phthalocyanine **Not measurablebecause of poor chargeability.

Table 1 shows that each photosensitive member according to the presentinvention exhibited an excellent sensitivity.

EXAMPLE 40

The electrophotographic photosensitive member prepared in Example 32 wassubjected to 5000 cycles of charging and exposure while setting initialdark-part potential Vd and light-part potential VI to ca. −700 volts andca. −150 volts respectively, thereby measuring a change in dark-partpotential ΔVd and a change in light-part potential ΔV1. The results areshown in Table 2 below together with those of Examples and ComparativeExample described below. In Table 2, +(plus) and −(minus) signspreceding the values of ΔVd and ΔV1 represents an increase and adecrease, respectively, in terms of absolute value of potential.

EXAMPLES 41-44

Photosensitive members (Nos. 6-7 and 10-11) prepared in Examples 34, 35,38 and 39, respectively were subjected to the charging-exposure cycletest in the same manner as in Example 40. The results are also shown inTable 2.

COMPARATIVE EXAMPLE 3

A photosensitive member (No. 12) prepared in Comparative Example 1 wassubjected to the charging-exposure cycle test in the same manner as inExample 40. The results are also shown in Table 2.

TABLE 2 No. of photosensitive Example member ΔVd (V) ΔVl (V) Ex. 40 4 −5−15 Ex. 41 6 −10  −10 Ex. 42 7  0  0 Ex. 43 10   0  −5 Ex. 44 11  −5 −10Comp. 12  −110  +105  Ex. 3 

The results in Table 2 above show that each photosensitive memberaccording to the present invention exhibited little potentialfluctuation in repetition of electrophotographic cycles.

EXAMPLE 45

An aluminum vapor-deposited polyethylene terephthalate film was providedwith a 0.5 μm-thick undercoating layer of polyvinyl alcohol on itsaluminum-deposited surface and further a 0.2 μm-thick charge generationlayer of the same composition as in Example 35.

Then, a solution of 5 parts of styryl compound of the following formula:

and 5 parts of polycarbonate resin (“Z-200” (trade name), mfd. byMitsubishi Kagaku K.K.) in 40 parts of tetrahydrofuran was applied ontothe charge generation layer and dried to form a 16 μm-thick chargetransport layer, thereby providing an electrophotographic photosensitivemember.

The thus-prepared photosensitive member was evaluated with respect tosensitivity and potential stability in the same manner as in Examples 29and 40, whereby the following results were obtained.

Sensitivity=0.32 μJ/cm²

ΔVd=0 volt

ΔV=−5 volts

EXAMPLE 46

An aluminum vapor-deposited polyethylene terephthalate film was providedwith a 0.5 μm-thick undercoating layer of polyvinyl alcohol on itsaluminum-deposited surface and further a 0.2 μm-thick charge generationlayer of the same composition as in Example 38.

Then, a solution of 5 parts of benzidine compound of the followingformula:

and 5 parts of polycarbonate resin (“Z-200” (trade name), mfd. byMitsubishi Kagaku K.K.) in 40 parts of tetrahydrofuran was applied ontothe charge generation layer and dried to form a 16 μm-thick chargetransport layer, thereby providing an electrophotographic photosensitivemember.

The thus-prepared photosensitive member was evaluated with respect tosensitivity and potential stability in the same manner as in Examples 29and 40, whereby the following results were obtained.

Sensitivity=0.43 μJ/cm²

ΔVd=0 volt

ΔV1=+10 volts

EXAMPLE 47

41 parts of phthalonitrile, 25 parts of gallium tribromide and 200 partsof α-chloronaphthalene were stirred for 4 hours under heating at 200° C.in a nitrogen atmosphere, followed by cooling to 130° C. and filtration.The recovered solid was washed with 200 parts of N,N-dimethylformamideat 130° C. under stirring for 2 hours, and was washed with methanol on afilter, followed by drying to recover 23 parts of a crystal, which wasfound to comprise bromogallium phthalocyanine (f) with an X-raydiffraction pattern shown in FIG. 32. The crystal also exhibited thefollowing elementary analysis results (C₃₂H₁₆N₈GaBr):

C (%) H (%) N (%) Br (%) Calculated value 58.05 2.44 16.92 12.07Measured value 57.92 2.35 16.86 11.9 

EXAMPLE 48

5 parts of the crystal obtained in Example 47 was treated for 9 hours inan automatic mortar (“ANM-150” (trade name), available from Nitto KagakuK.K. and comprising a porcelain mortar and a porcelain pestle rotatingat fixed speeds of 6 rpm and 100 rpm, respectively, in mutually reversedirections) to provide a crystal, which was found to comprisebromogallium phthalocyanine (g) with an X-ray diffraction pattern shownin FIG. 33.

EXAMPLE 49

0.3 part of the crystal obtained in Example 48, 10 parts of chloroformand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol and dryingto recover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 34.

EXAMPLE 50

0.3 part of the crystal obtained in Example 48, 10 parts ofcyclohexanone and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing-withmethanol and drying to recover a crystal, which was found to comprisebromogallium phthalocyanine (g) with an X-ray diffraction pattern shownin FIG. 35.

EXAMPLE 51

0.3 part of the crystal obtained in Example 48, 10 parts of acetonitrileand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol and dryingto recover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 36.

EXAMPLE 52

0.3 part of the crystal obtained in Example 48, 10 parts of butylacetate and 10 parts of 1 mm-dia. glass beads were dispersed for 24hours in a paint shaker, followed by filtration, washing with methanoland drying to recover a crystal, which was found to comprisebromogallium phthalocyanine (g) with an X-ray diffraction pattern shownin FIG. 37.

EXAMPLE 53

0.3 part of the crystal obtained in Example 48, 10 parts of ethyleneglycol and 10 parts of 1 mm-dia. glass beads were dispersed for 24 hoursin a paint shaker, followed by filtration, washing with methanol anddrying to recover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 38.

EXAMPLE 54

0.3 part of the crystal obtained in Example 48, 10 parts ofmono-chlorobenzene and 10 parts of 1 mm-dia. glass beads were dispersedfor 24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisebromogallium phthalocyanine (g) with an X-ray diffraction pattern shownin FIG. 39.

EXAMPLE 55

0.3 part of the crystal obtained in Example 48, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24.hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisebromogallium phthalocyanine (g) with an X-ray diffraction pattern shownin FIG. 40.

EXAMPLE 56

0.3 part of the crystal obtained in Example 48, 10 parts of methyl ethylketone and 10 parts of 1 mm-dia. glass beads were dispersed for 24 hoursin a paint shaker, followed by filtration, washing with methanol anddrying to recover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 41.

EXAMPLE 57

0.3 part of the crystal obtained in Example 48, 10 parts of methanol and10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in a paintshaker, followed by filtration, washing with methanol and drying torecover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 42.

EXAMPLE 58

0.3 part of the crystal obtained in Example 48, 10 parts ofN,N-dimethylformamide and 10 parts of 1 mm-dia. glass beads weredispersed for 24 hours in a paint shaker, followed by filtration,washing with methanol and drying to recover a crystal, which was foundto comprise bromogallium phthalocyanine (h) with an X-ray diffractionpattern shown in FIG. 43.

EXAMPLE 59

0.3 part of the crystal obtained in Example 48, 10 parts ofN,N-diethylaniline and 10 parts of 1 mm-dia. glass beads were dispersedfor 24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisebromogallium phthalocyanine (i) with an X-ray diffraction pattern shownin FIG. 44.

EXAMPLE 60

3 parts of the crystal obtained in Example 47 and 120 parts of 1 m-dia.glass beads were dispersed for 24 hours in a paint shaker, followed byan ultrasonic treatment in water, filtration and drying to obtain acrystal, which was found to comprise bromogallium phthalocyanine (h)with an X-ray diffraction pattern of FIG. 45.

EXAMPLE 61

3 parts of the crystal obtained in Example 47 and 120 parts of 1 mm-dia.glass beads were dispersed for 24 hours in a paint shaker, followed byan ultrasonic treatment in water, filtration and drying to obtain acrystal, which was found to comprise bromogallium phthalocyanine (h)with an X-ray diffraction pattern of FIG. 46.

EXAMPLE 62

0.3 part of the crystal obtained in Example 60, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisebromogallium phthalocyanine (g) with an X-ray diffraction pattern shownin FIG. 47.

EXAMPLE 63

0.3 part of the crystal obtained in Example 60, 10 parts of chloroformand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol and dryingto recover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 48.

The crystal also exhibited the following elementary analysis results(C₃₂H₁₆N₈GaBr):

C (%) H (%) N (%) Calculated value 58.05 2.44 16.92 Measured value 58.162.39 16.86

EXAMPLE 64

0.3 part of the crystal obtained in Example 60, 10 parts of methanol and10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in a paintshaker, followed by filtration, washing with methanol and drying torecover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 49.

EXAMPLE 65

0.3 part of the crystal obtained in Example 61, 10 parts of methanol and10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in a paintshaker, followed by filtration, washing with methanol and drying torecover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 50.

EXAMPLE 66

0.3 part of the crystal obtained in Example 60, 10 parts ofN,N-dimethylformamide and 10 parts of 1 m-dia. glass beads weredispersed for 3 hours in a paint shaker, followed by filtration, washingwith methanol and drying to recover a crystal, which was found tocomprise bromogallium phthalocyanine (h) with an X-ray diffractionpattern shown in FIG. 51.

EXAMPLE 67

0.3 part of the crystal obtained in Example 60, 10 parts ofN,N-dimethylformamide and 10 parts of 1 mm-dia. glass beads weredispersed for 24 hours in a paint shaker, followed by filtration,washing with methanol and drying to recover a crystal, which was foundto comprise bromogallium phthalocyanine (h) with an X-ray diffractionpattern shown in FIG. 52.

The crystal also exhibited the following elementary analysis results(C₃₂H₁₆N₈GaBr):

C (%) H (%) N (%) Calculated value 58.05 2.44 16.92 Measured value 57.182.61 16.08

EXAMPLE 68

0.3 part of hydroxygallium phthalocyanine (with an X-ray diffractionpattern of FIG. 53), 10 parts of 1 N-hydrobromic acid aqueous solutionand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol an drying torecover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 54.

The crystal also exhibited the following elementary analysis results(C₃₂H₁₆N₈GaBr):

C (%) H (%) N (%) Calculated value 58.05 2.44 16.92 Measured value 56.982.36 16.30

EXAMPLE 69

0.3 part of hydroxygallium phthalocyanine (with an X-ray diffractionpattern of FIG. 53), 10 parts of 2 N-hydrobromic acid aqueous solutionand 10 parts of 1 mi-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol an drying torecover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern shown in FIG. 55.

EXAMPLE 70

0.3 part of hydroxygallium phthalocyanine (with an X-ray diffractionpattern of FIG. 56), 10 parts of 1 N-hydrobromic acid aqueous solutionand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol an drying torecover a crystal, which was found to comprise bromogalliumphthalocyanine (g) with an X-ray diffraction pattern similar to the oneshown in FIG. 54.

EXAMPLE 71

0.3 part of the crystal obtained in Example 68, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisebromogallium phthalocyanine (g) with an X-ray diffraction pattern shownin FIG. 57.

The crystal also exhibited the following elementary analysis results(C₃₂H₁₆N₈GaBr):

C (%) H (%) N (%) Calculated value 58.05 2.44 16.92 Measured value 57.562.29 16.34

EXAMPLE 72

0.3 part of the crystal obtained in Example 68, 10 parts ofN,N-dimethylformamide and 10 parts of 1mm-dia. glass beads weredispersed for 24 hours in a paint shaker, followed by filtration,washing with methanol and drying to recover a crystal, which was foundto comprise bromogallium phthalocyanine (h) with an X-ray diffractionpattern shown in FIG. 58.

The crystal also exhibited the following elementary analysis results(C₃₂H₁₆N₈GaBr):

C (%) H (%) N (%) Calculated value 58.05 2.44 16.92 Measured value 57.652.73 16.08

EXAMPLE 73

3 parts of the crystal obtained in Example 68 was stirred in 100 partsof sodium bicarbonate aqueous solution (pH 10), followed by sufficientwashing with distilled water, filtration, washing with methanol anddrying to recover a crystal, which was found to comprise bromogalliumphthalocyanine (j) with an X-ray diffraction pattern shown in FIG. 59.

Hereinbelow, some examples for preparation of electrophotographicphotosensitive members by using bromogallium phthalocyanines preparedabove will be described.

EXAMPLE 74

An aluminum substrate was coated with a solution of 5 g ofmethoxymethylated nylon resin (Mw (weight−average molecularweight)=3.2×10⁴) and 10 g of alcohol-soluble copolymer nylon(Mw=2.9×10⁴) in 95 g of methanol by using a wire bar and dried to form a1 μm-thick undercoating layer.

Then, 3 parts of the bromogallium phthalocyanine (f) prepared in Example1 was added to a solution of 2 parts of polyvinylbutyral in 60 parts ofcyclohexanone, and the mixture was dispersed together with 100 parts of1 mm-dia. glass beads for 3 hours in a sand mill. The resultantdispersion was further diluted with 100 parts of ethyl acetate, andapplied by a wire bar over the undercoating layer, followed by drying toform a 0.2 μm-thick charge generation layer.

Then, a solution of 5 parts of a triarylamine compound of the followingformula:

and 5 parts of polycarbonate resin (“Z-200” (trade name), mfd. byMitsubishi Kagaku K.K.) in 35 parts of chlorobenzene was applied by awire bar onto the charge generation layer and dried to form a 18μm-thick charge transport layer, thereby providing anelectrophotographic photosensitive member.

EXAMPLES 75-84

Electrophotographic photosensitive members were prepared in the samemanner as in Example 74 except for using bromogallium phthalocyaninesprepared in the respective Examples shown in Table 3 below as chargegeneration materials instead of bromogallium phthalocyanine (f) preparedin Example 47.

COMPARATIVE EXAMPLE 4

An electrophotographic photosensitive member was prepared in the samemanner as in Example 74 except for using ε-form copper phthalocyanine asa charge generation material instead of bromogallium phthalocyanine (f)prepared in Example 47.

COMPARATIVE EXAMPLE 5

An electrophotographic photosensitive member was prepared in the samemanner as in Example 74 except for using hydroxygallium phthalocyanine(with an X-ray diffraction pattern of FIG. 53) as a charge generationmaterial instead of bromogallium phthalocyanine (f) prepared in Example47.

Each of the above-prepared photosensitive members was applied onto analuminum cylinder to form a photosensitive drum, which was incorporatedin a laser beam printer (“LBX-SX” (trade name), mfd. by Canon K.K.) andsubjected to a sensitivity measurement wherein the photosensitive memberwas first charged to a dark-part potential of −700 volts and illuminatedwith laser light at a wavelength of 802 nm, thereby measuring a lightquantity required to lower the potential of −700 volts down to alight-part potential of −150 volts as a sensitivity.

The results are inclusively shown in Table 3 below.

TABLE 3 No. of Bromogallium photosensitive phthalocyanine SensitivityExample member (Ex. No.) (μJ/cm²) Ex. 74 13 (f) (Ex. 47) 0.90 Ex. 75 14(g) (Ex. 48) 1.02 Ex. 76 15 (g) (Ex. 50) 0.75 Ex. 77 16 (h) (Ex. 58)2.24 Ex. 78 17 (i) (Ex. 59) 0.54 Ex. 79 18 (h) (Ex. 60) 1.04 Ex. 80 19(g) (Ex. 63) 0.96 Ex. 81 20 (h) (Ex. 67) 0.46 Ex. 82 21 (g) (Ex. 68)0.42 Ex. 83 22 (g) (Ex. 71) 1.00 Ex. 84 23 (j) (Ex. 73) 2.12 Comp. 24ε-Cu 2.25 Ex. 4  Comp. 25 Hydroxygallium ** Ex. 5  phthalocyanine **Notmeasurable because of poor chargeability.

Table 3 shows that each photosensitive member according to the presentinvention exhibited an excellent sensitivity.

EXAMPLE 85

The electrophotographic photosensitive member prepared in Example 75 wassubjected to 5000 cycles of charging and exposure while setting initialdark-part potential Vd and light-part potential V1 to ca. −700 volts andca. −150 volts respectively, thereby measuring a change in dark-partpotential ΔVd and a change in light-part potential ΔV1. The results areshown in Table 4 below together with those of Examples and ComparativeExample described below. In Table 4, +(plus) and −(minus) signspreceding the values of ΔVd and ΔV1 represents an increase and adecrease, respectively, in terms of absolute value of potential.

EXAMPLES 86-89

Photosensitive members (Nos. 16, 18, 20 and 21) prepared in Examples 77,79, 81 and 82, respectively were subjected to the charging-exposurecycle test in the same manner as in Example 85. The results are alsoshown in Table 4.

COMPARATIVE EXAMPLE 6

A photosensitive member (No. 24) prepared in Comparative Example 4 wassubjected to the charging-exposure cycle test in the same manner as inExample 85. The results are also shown in Table 4.

TABLE 4 No. of photosensitive Example member ΔVd (V) ΔVl (V) Ex. 85 14 0 +15 Ex. 86 16 −10  +15 Ex. 87 18 −5 −10 Ex. 88 20  0 +20 Ex. 89 21 −5+10 Comp. 24 −110  +105  Ex. 6 

The results in Table 4 above show that each photosensitive memberaccording to the present invention exhibited little potentialfluctuation in repetition of electrophotographic cycles.

EXAMPLE 90

An aluminum vapor-deposited polyethylene terephthalate film was providedwith a 0.5 μm-thick undercoating layer of polyvinyl alcohol on itsaluminum-deposited surface and further a 0.2 μm-thick charge generationlayer of the same composition as in Example 82.

Then, a solution of 5 parts of styryl compound of the following formula:

and 5 parts of polycarbonate resin (“Z-200” (trade name), mfd. byMitsubishi Kagaku K.K.) in 40 parts of tetrahydrofuran was applied ontothe charge generation layer and dried to form a 16 μm-thick chargetransport layer, thereby providing an electrophotographic photosensitivemember.

The thus-prepared photosensitive member was evaluated with respect tosensitivity and potential stability in the same manner as in Examples 74and 85, whereby the following results were obtained.

Sensitivity=0.47 μJ/cm²

ΔVd=−10 volts

ΔV1=+20 volts

EXAMPLE 91

An aluminum vapor-deposited polyethylene terephthalate film was providedwith a 0.5 μm-thick undercoating layer of polyvinyl alcohol on itsaluminum-deposited surface and further a 0.2 μm-thick charge generationlayer of the same composition as in Example 67.

Then, a solution of 5 parts of benzidine compound of the followingformula:

and 5 parts of polycarbonate resin (“Z-200” (trade name), mfd. byMitsubishi Kagaku K.K.) in 40 parts of tetrahydrofuran was applied ontothe charge generation layer and dried to form a 16 μm-thick chargetransport layer, thereby providing an electrophotographic photosensitivemember.

The thus-prepared photosensitive member was evaluated with respect tosensitivity and potential stability in the same manner as in Examples 74and 85, whereby the following results were obtained.

Sensitivity=0.47 μJ/cm²

ΔVd=−5 volts

ΔV1=+30 volts

EXAMPLE 92

22 parts of phthalonitrile, 10 parts of zirconium tetrachloride and 100parts of quinoline were stirred for 4 hours under heating at 180° C. ina nitrogen atmosphere, followed by cooling to 130° C. and filtration.The recovered solid was subjected to 3 times of washing with 200 partsof N,N-dimethylformamide at 130° C. for 2 hours under stirring, followedby filtration, washing with methanol on the filter and drying to obtaina crystal, which was found to comprise zirconium phthalocyanine with anX-ray diffraction pattern shown in FIG. 60 showing strong peaks at Braggangles (2θ) of 7.8 deg., 8.0 deg. and 8.2 deg. The zirconiumphthalocyanine also exhibited an infrared-absorption spectrum shown inFIG. 76.

The compound also exhibited a mass spectrum value (FAB-MS, matrix: NBA)of 619 (m/Z) and the following elementary analysis results(C₃₂H₁₈N₈O₂Zr):

C (%) H (%) N (%) Calculated value 60.26 2.84 17.57 Measured value 58.333.02 16.82

EXAMPLE 93

22 parts of phthalonitrile, 40 parts of zirconium tetrachloride and 440parts of quinoline were stirred for 4 hours under heating at 180° C. ina nitrogen atmosphere, followed by cooling to 130° C. and filtration.The recovered solid was subjected to 3 times of washing with 200 partsof N,N-dimethylformamide at 130° C. for 2 hours under stirring, followedby filtration, washing with methanol on the filter and drying to obtaina crystal, which was found to comprise zirconium phthalocyanine with anX-ray diffraction pattern shown in FIG. 61 showing strong peaks at Braggangles (2θ) of 8.0 deg. and 8.2 deg. The zirconium phthalocyanine alsoexhibited an infrared-absorption spectrum shown in FIG. 77.

The compound also exhibited a mass spectrum value (FAB-MS, matrix: NBA)of 619 (m/Z) and the following elementary analysis results(C₃₂H₁₈N₈O₂Zr):

C (%) H (%) N (%) Calculated value 60.26 2.84 17.57 Measured value 59.562.78 17.35

EXAMPLE 94

0.3 part of the crystal obtained in Example 92, 10 parts ofN,N-dimethylformamide and 10 parts of 1 in-dia. glass beads weredispersed for 24 hours in a paint shaker, followed by filtration,washing with methanol and drying to recover a crystal, which was foundto comprise zirconium phthalocyanine with an X-ray diffraction patternshown in FIG. 62 showing a strong peak at a Bragg angle (2θ) of 8.0 deg.

EXAMPLE 95

0.3 part of the crystal obtained in Example 92, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisezirconium phthalocyanine with an X-ray diffraction pattern shown in FIG.63 showing a strong peak at a Bragg angle (2θ) of 8.1 deg.

EXAMPLE 96

0.3 part of the crystal obtained in Example 92, 10 parts of methanol and10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in a paintshaker, followed by filtration, washing with methanol and drying torecover a crystal, which was found to comprise zirconium phthalocyaninewith an X-ray diffraction pattern shown in FIG. 64 showing a strong peakat a Bragg angle (2θ) of 8.1 deg.

EXAMPLE 97

0.3 part of the crystal obtained in Example 92, 10 parts ofmonochlorobenzene and 10 parts of 1 mm-dia. glass beads were dispersedfor 24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisezirconium phthalocyanine with an X-ray diffraction pattern shown in FIG.65 showing a strong peak at a Bragg angle (2θ) of 8.0 deg.

EXAMPLE 98

0.3 part of the crystal obtained in Example 93, 10 parts ofN,N-dimethylformamide and 10 parts of 1 m-dia. glass beads weredispersed for 24 hours in a paint shaker, followed by filtration,washing with methanol and drying to recover a crystal, which was foundto comprise zirconium phthalocyanine with an X-ray diffraction patternshown in FIG. 66 showing a strong peak at a Bragg angle (2θ) of 7.9 deg.

EXAMPLE 99

0.3 part of the crystal obtained in Example 93, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisezirconium phthalocyanine with an X-ray diffraction pattern shown in FIG.67 showing a strong peak at a Bragg angle (2θ) of 8.0 deg.

EXAMPLE 100

0.3 part of the crystal obtained in Example 93, 10 parts of chloroformand 10 parts of 1 mm-dia. glass beads were dispersed for 24 hours in apaint shaker, followed by filtration, washing with methanol and dryingto recover a crystal, which was found to comprise zirconiumphthalocyanine with an X-ray diffraction pattern shown in FIG. 68showing a strong peak at a Bragg angle (2θ) of 8.1 deg.

EXAMPLE 101

0.3 part of the crystal obtained in Example 93, 10 parts ofmonochlorobenzene and 10 parts of 1 mm-dia. glass beads were dispersedfor 24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisezirconium phthalocyanine with an X-ray diffraction pattern shown in FIG.69 showing strong peaks at Bragg angles (2θ) of 7.9 deg. and 8.7 deg.

REFERENCE EXAMPLE

3 parts of the crystal obtained in Example 93 and 120 parts of 1 mm-dia.glass beads were dispersed for 24 hours in a paint shaker, followed byultrasonic treatment in water, filtration and drying to recoverzirconium phthalocyanine with an X-ray diffraction pattern shown in FIG.70.

EXAMPLE 102

0.3 part of rather amorphous zirconium phthalocyanine obtained inReference Example, 10 parts of N,N-dimethylformamide and 10 parts of 1mm-dia. glass beads were dispersed for 24 hours in a paint shaker,followed by filtration, washing with methanol and drying to recover acrystal, which was found to comprise zirconium phthalocyanine with anX-ray diffraction pattern shown in FIG. 71 showing strong peaks at Braggangle (2θ) of 7.7 deg. and 8.2 deg.

EXAMPLE 103

0.3 part of the crystal obtained in Example 93, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisezirconium phthalocyanine with an X-ray diffraction pattern shown in FIG.72 showing a strong peak at a Bragg angle (2θ) of 8.0 deg.

EXAMPLE 104

5 parts of the crystal obtained in Example 93 was treated for 4 hours inan automatic mortar (“ANM-150” (trade name), available from Nitto KagakuK.K. and comprising a porcelain mortar and a porcelain pestle rotatingat fixed speeds of 6 rpm and 100 rpm, respectively, in mutually reversedirections) to recover a crystal, which was found to comprise zirconiumphthalocyanine with an X-ray diffraction pattern shown in FIG. 73showing strong peaks at 7.8 deg., 8.0 deg. and 8.2 deg.

EXAMPLE 105

0.3 part of the crystal obtained in Example 104, 10 parts oftetrahydrofuran and 10 parts of 1 mm-dia. glass beads were dispersed for24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisezirconium phthalocyanine with an X-ray diffraction pattern shown in FIG.74 showing a strong peak at a Bragg angle (2θ) of 8.0 deg.

EXAMPLE 106

0.3 part of the crystal obtained in Example 104, 10 parts ofmonochlorobenzene and 10 parts of 1 mm-dia. glass beads were dispersedfor 24 hours in a paint shaker, followed by filtration, washing withmethanol and drying to recover a crystal, which was found to comprisezirconium phthalocyanine with an X-ray diffraction pattern shown in FIG.75 showing a strong peak at a Bragg angle (2θ) of 8.0 deg.

Hereinbelow, some examples for preparation of electrophotographicphotosensitive members by using zirconium phthalocyanines prepared abovewill be described.

EXAMPLE 107

An aluminum substrate was coated with a solution of 5 g ofmethoxymethylated nylon resin (Mw (weight−average molecularweight)=3.2×10⁴) and 10 g of alcohol-soluble copolymer nylon(Mw=2.9×10⁴) in 95 g of methanol by using a wire bar and dried to form a1 μm-thick undercoating layer.

Then, 3 parts of the zirconium phthalocyanine prepared in Example 94 wasadded to a solution of 2 parts of polyvinylbutyral in 60 parts ofcyclohexanone, and the mixture was dispersed together with 100 parts of1 mm-dia. glass beads for 3 hours in a sand mill. The resultantdispersion was further diluted with 100 parts of ethyl acetate, andapplied by a wire bar over the undercoating layer, followed by drying toform a 0.2 μm-thick charge generation layer.

Then, a solution of 5 parts of a triarylamine compound of the followingformula:

and 5 parts of polycarbonate resin (“Z-200” (trade name), mfd. byMitsubishi Kagaku K.K.) in 35 parts of chlorobenzene was applied by awire bar onto the charge generation layer and dried to form a 19μm-thick charge transport layer, thereby providing anelectrophotographic photosensitive member.

EXAMPLES 108-117

Electrophotographic photosensitive members were prepared in the samemanner as in Example 107 except for using zirconium phthalocyanineprepared in the respective Examples shown in Table 5 below as chargegeneration materials instead of zirconium phthalocyanine prepared inExample 94.

COMPARATIVE EXAMPLE 7

An electrophotographic photosensitive member was prepared in the samemanner as in Example 107 except for using ε-form copper phthalocyanineas a charge generation material instead of the zirconium phthalocyanineprepared in Example 94.

Each of the above-prepared photosensitive members was applied onto analuminum cylinder to form a photosensitive drum, which was incorporatedin a laser beam printer (“LBX-SX” (trade name), mfd. by Canon K.K.) andsubjected to a sensitivity measurement wherein the photosensitive memberwas first charged to a dark-part potential of −700 volts and illuminatedwith laser light at a wavelength of 802 nm, thereby measuring a lightquantity E_(½) required to lower the potential of −700 volts down to ahalf (−350 volts) as a sensitivity.

The results are inclusively shown in Table 5 below.

TABLE 5 No. of Zirconium photosensitive phthalocyanine E_(½) Examplemember Ex. No. (μJ/cm²) Ex. 107 26 (Ex. 94)  1.00 Ex. 108 27 (Ex. 95) 0.75 Ex. 109 28 (Ex. 97)  0.60 Ex. 110 29 (Ex. 98)  1.40 Ex. 111 30 (Ex.99)  0.82 Ex. 112 31 (Ex. 100) 0.75 Ex. 113 32 (Ex. 101) 0.49 Ex. 114 33(Ex. 102) 1.50 Ex. 115 34 (Ex. 103) 0.75 Ex. 116 35 (Ex. 104) 0.58 Ex.117 36 (Ex. 105) 1.05 Comp. 37 ε-Cu 1.42 Ex. 7 

Table 5 shows that each photosensitive member according to the presentinvention exhibited an excellent sensitivity.

EXAMPLE 118

The electrophotographic photosensitive member prepared in Example 108was subjected to 5000 cycles of charging and exposure while settinginitial dark-part potential Vd and light-part potential V1 to ca. −700volts and ca. −150 volts respectively, thereby measuring a change indark-part potential ΔVd and a change in light-part potential ΔV1. Theresults are shown in Table 2 below together with those of Examples andComparative Example described below. In Table 2, +(plus) and −(minus)signs preceding the values of ΔVd and ΔV1 represents an increase and adecrease, respectively in terms of absolute value of potential.

EXAMPLES 119-122

Photosensitive members (Nos. 28, 32, 34 and 35) prepared in Examples109, 113, 115 and 116, respectively were subjected to thecharging-exposure cycle test in the same manner as in Example 118. Theresults are also shown in Table 6.

COMPARATIVE EXAMPLE 8

A photosensitive member (No. 37) prepared in Comparative Example 7 wassubjected to the charging-exposure cycle test in the same manner as inExample 118. The results are also shown in Table 6.

TABLE 6 No. of photosensitive Example member ΔVd (V) ΔVl (V) Ex. 118 27−5 +10 Ex. 119 29 −5  +5 Ex. 120 32  0  +5 Ex. 121 33 +5 +10 Ex. 122 35−5 +10 Comp. 37 −110  +120  Ex. 8 

The results in Table 6 above show that each photosensitive memberaccording to the present invention exhibited little potentialfluctuation in repetition of electrophotographic cycles.

EXAMPLE 123

An aluminum vapor-deposited polyethylene terephthalate film was providedwith a 0.5 μm-thick undercoating layer of polyvinyl alcohol on itsaluminum-deposited surface and further a 0.2 μm-thick charge generationlayer of the same composition as in Example 116.

Then, a solution of 5 parts of styryl compound of the following formula:

and 5 parts of polycarbonate resin (“Z-200” (trade name), mfd. byMitsubishi Kagaku K.K.) in 40 parts of tetrahydrofuran was applied ontothe charge generation layer and dried to form a 16 μm-thick chargetransport layer, thereby providing an electrophotographic photosensitivemember.

The thus-prepared photosensitive member was evaluated with respect tosensitivity and potential stability in the same manner as in Examples107 and 118, whereby the following results were obtained.

E_(½)=0.60 μJ/cm²

ΔVd=−5 volts

ΔV1 =+10 volts

EXAMPLE 124

An aluminum vapor-deposited polyethylene terephthalate film was providedwith a 0.5 μm-thick undercoating layer of polyvinyl alcohol on itsaluminum-deposited surface and further a 0.2 μm-thick charge generationlayer of the same composition as in Example 108.

Then, a solution of 5 parts of benzidine compound of the followingformula:

and 5 parts of polycarbonate resin (“Z-200” (trade name), mfd. byMitsubishi Kagaku K.K.) in 40 parts of tetrahydrofuran was applied ontothe charge generation layer and dried to form a 25 μm-thick chargetransport layer, thereby providing an electrophotographic photosensitivemember.

The thus-prepared photosensitive member was evaluated with respect tosensitivity and potential stability in the same manner as in Examples107 and 118, whereby the following results were obtained.

E_(½)=0.40 μJ/cm²

ΔVd=0 volt

ΔV1=+15 volts

What is claimed is:
 1. An electrophotographic photosensitive member,comprising a support, and a photosensitive layer formed on the support;said photosensitive layer containing iodogallium phthalocyanine having acrystal form selected from those characterized by X-ray diffractionpatterns (a)-(e) shown below respectively obtained by a CuKαcharacteristic X-ray diffraction method: (a) having a strongest peak ata Bragg angle (2θ±0.2 deg.) of 9.6 deg. and free from another peakhaving an intensity of 30% or more of that of the strongest peak, (b)having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 9.4 deg. and 27.1 deg. wherein the second strongestpeak has an intensity of at least 30% of that of the strongest peak, (c)having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 7.5 deg. and 27.7 deg., (d) having a strongest peak anda second strongest peak at Bragg angles (2θ±0.2 deg.) of 7.5 deg. and26.4 deg., and (e) having two peaks among a strongest peak, a secondstrongest peak and a third strongest peak at Bragg angles (2θ±0.2 deg.)of 8.8 deg. and 27.2 deg.
 2. A photosensitive member according to claim1, wherein the iodogallium phthalocyanine has a crystal formcharacterized by the X-ray diffraction pattern (a).
 3. A photosensitivemember according to claim 1, wherein the iodogallium phthalocyanine hasa crystal form characterized by the X-ray diffraction pattern (b).
 4. Aphotosensitive member according to claim 3, wherein the X-raydiffraction pattern (b) further shows strong peaks at Bragg angles(2θ±0.2 deg.) of 8.7 deg., 16.4 deg., 18.3 deg. and 19.5 deg.
 5. Aphotosensitive member according to claim 1, wherein the iodogalliumphthalocyanine has a crystal form characterized by the X-ray diffractionpattern (c).
 6. A photosensitive member according to claim 5, whereinthe X-ray diffraction pattern (c) further shows a strong peak at a Braggangle (2θ±0.2 deg.) of 16.3 deg.
 7. A photosensitive member according toclaim 1, wherein the iodogallium phthalocyanine has a crystal formcharacterized by the X-ray diffraction pattern (d).
 8. A photosensitivemember according to claim 7, wherein the X-ray diffraction pattern (d)further shows a strong peak at a Bragg angle (2θ±0.2 deg.) of 16.3 deg.9. A photosensitive member according to claim 1, wherein the iodogalliumphthalocyanine has a crystal form characterized by the X-ray diffractionpattern (e).
 10. A photosensitive member according to claim 9, whereinthe X-ray diffraction pattern (e) further shows a strong peak at a Braggangle (2θ±0.2 deg.) of 9.8 deg.
 11. An electrophotographicphotosensitive member, comprising a support, and a photosensitive layerformed on the support; said photosensitive layer containing bromogalliumphthalocyanine having a crystal form selected from those represented byX-ray diffraction patterns (f)-(j) shown below respectively obtained bya CuKα characteristic X-ray diffraction method: (f) having a strongestpeak at a Bragg angle (2θ±0.2 deg.) of 27.3 deg. and free from anotherpeak having an intensity of 30% or more of that of the strongest peak,(g) having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 9.0 deg. and 27.1 deg., wherein the second strongestpeak has an intensity of at least 30% of that of the strongest peak, (h)having a strongest peak and a second strongest peak at Bragg angles(2θ±0.2 deg.) of 7.4 deg. and 27.9 deg., (i) having a strongest peak anda second strongest peak at Bragg angles (2θ±0.2 deg.) of 7.5 deg. and26.4 deg., and (j) having a strongest peak and a second strongest peakat Bragg angles (2θ±0.2 deg.) of 6.9 deg. and 26.7 deg.
 12. Aphotosensitive member according to claim 11, wherein the bromogalliumphthalocyanine has a crystal form characterized by the X-ray diffractionpattern (f).
 13. A photosensitive member according to claim 11, whereinthe bromogallium phthalocyanine has a crystal form characterized by theX-ray diffraction pattern (g).
 14. A photosensitive member according toclaim 13, wherein the X-ray diffraction pattern (g) further shows strongpeaks at Bragg angles (2θ±0.2 deg.) of 9.7 deg., 18.2 deg. and 21.0 deg.15. A photosensitive member according to claim 11, wherein thebromogallium phthalocyanine has a crystal form characterized by theX-ray diffraction pattern (h).
 16. A photosensitive member according toclaim 15, wherein the X-ray diffraction pattern (h) further shows astrong peak at a Bragg angle (2θ±0.2 deg.) of 16.2 deg.
 17. Aphotosensitive member according to claim 11, wherein the bromogalliumphthalocyanine has a crystal form characterized by the X-ray diffractionpattern (i).
 18. A photosensitive member according to claim 17, whereinthe X-ray diffraction pattern (i) further shows strong peaks at Braggangles (2θ±0.2 deg.) of 16.3 deg and 24.9 deg.
 19. A photosensitivemember according to claim 11, wherein the bromogallium phthalocyaninehas a crystal form characterized by the X-ray diffraction pattern (j).20. A photosensitive member according to claim 19, wherein the X-raydiffraction pattern (j) further shows strong peaks at Bragg angles(2θ±0.2 deg.) of 13.6 deg. and 16.6 deg.
 21. An electrophotographicphotosensitive member comprising a support and a photosensitive layerformed on the support, said photosensitive layer containing zirconiumphthalocyanine having a crystal from represented by an X-ray diffractionpattern having a strongest peak at a Bragg angle (2θ±0.2 deg.) in arange of 7.0-9.0 deg. as measured by a CuKα characteristic X-raydiffraction method.
 22. An electrophotographic photosensitive memberaccording to claim 21, wherein the strongest peak is at a Bragg angle(2θ±0.2 deg.) of 8.0 deg.
 23. An electrophotographic photosensitivemember according to claim 21 or 22, wherein the X-ray diffractionpattern further shows a strong peak at a Bragg angle (2θ±2.0 deg.) of25.5 deg.